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WO2023115637A1 - Preparation, product and use of biomass-based nitrogen-doped graphene/nano carbon fiber axial composite material loaded with monatomic iron - Google Patents

Preparation, product and use of biomass-based nitrogen-doped graphene/nano carbon fiber axial composite material loaded with monatomic iron Download PDF

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WO2023115637A1
WO2023115637A1 PCT/CN2021/143577 CN2021143577W WO2023115637A1 WO 2023115637 A1 WO2023115637 A1 WO 2023115637A1 CN 2021143577 W CN2021143577 W CN 2021143577W WO 2023115637 A1 WO2023115637 A1 WO 2023115637A1
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bacterial cellulose
iron
doped graphene
nitrogen
urea
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PCT/CN2021/143577
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French (fr)
Chinese (zh)
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崔大祥
王敬锋
肖龙飞
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上海纳米技术及应用国家工程研究中心有限公司
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Publication of WO2023115637A1 publication Critical patent/WO2023115637A1/en

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    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B82—NANOTECHNOLOGY
    • B82Y—SPECIFIC USES OR APPLICATIONS OF NANOSTRUCTURES; MEASUREMENT OR ANALYSIS OF NANOSTRUCTURES; MANUFACTURE OR TREATMENT OF NANOSTRUCTURES
    • B82Y30/00—Nanotechnology for materials or surface science, e.g. nanocomposites
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B82—NANOTECHNOLOGY
    • B82Y—SPECIFIC USES OR APPLICATIONS OF NANOSTRUCTURES; MEASUREMENT OR ANALYSIS OF NANOSTRUCTURES; MANUFACTURE OR TREATMENT OF NANOSTRUCTURES
    • B82Y40/00—Manufacture or treatment of nanostructures
    • C—CHEMISTRY; METALLURGY
    • C25—ELECTROLYTIC OR ELECTROPHORETIC PROCESSES; APPARATUS THEREFOR
    • C25B—ELECTROLYTIC OR ELECTROPHORETIC PROCESSES FOR THE PRODUCTION OF COMPOUNDS OR NON-METALS; APPARATUS THEREFOR
    • C25B1/00—Electrolytic production of inorganic compounds or non-metals
    • C25B1/01—Products
    • C25B1/02—Hydrogen or oxygen
    • C25B1/04—Hydrogen or oxygen by electrolysis of water
    • C—CHEMISTRY; METALLURGY
    • C25—ELECTROLYTIC OR ELECTROPHORETIC PROCESSES; APPARATUS THEREFOR
    • C25B—ELECTROLYTIC OR ELECTROPHORETIC PROCESSES FOR THE PRODUCTION OF COMPOUNDS OR NON-METALS; APPARATUS THEREFOR
    • C25B11/00—Electrodes; Manufacture thereof not otherwise provided for
    • C25B11/04—Electrodes; Manufacture thereof not otherwise provided for characterised by the material
    • C25B11/051—Electrodes formed of electrocatalysts on a substrate or carrier
    • C25B11/073—Electrodes formed of electrocatalysts on a substrate or carrier characterised by the electrocatalyst material
    • C25B11/091—Electrodes formed of electrocatalysts on a substrate or carrier characterised by the electrocatalyst material consisting of at least one catalytic element and at least one catalytic compound; consisting of two or more catalytic elements or catalytic compounds

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  • the invention belongs to the field of preparation of nano metal-semiconductor composite materials, and in particular relates to a preparation method of biomass-based nitrogen-doped graphene/nano-carbon fiber axial composite material loaded with monoatomic iron and its product and application.
  • Hydrogen has both the advantages of high energy density and environmental friendliness. It is one of the important clean energy that meets the development requirements of human society and has a very broad application prospect. In a series of links that use hydrogen as an energy carrier and finally exert its efficacy, such as hydrogen production, hydrogen storage and hydrogen energy release, hydrogen production is undoubtedly a key.
  • the main way of industrial hydrogen production is hydrogen production from various fossil fuels, but this process will pollute the environment.
  • the reactants of hydrogen production by hydrolysis are the same as the products after hydrogen releases energy, the two reactions just form a closed loop, so hydrogen production by hydrolysis is the most environmentally friendly and recyclable hydrogen production method.
  • the catalyst with the best electrocatalytic hydrolysis hydrogen production effect is the noble metal Pt-based catalyst, but its low abundance and high price also restrict its wide application. The key to the development and utilization of hydrogen energy in the future.
  • graphene has become a key research object in the application of photocatalytic chemistry due to its high specific surface area, excellent electrical properties, abundant active sites and good stability.
  • people can enhance their selectivity to catalytic reactants, catalytic performance or both, and morphology control and heteroatom doping, etc.
  • the modification method is currently the most widely used means to adjust the properties of graphene.
  • the modification method of heteroatom doping The commonly used doping atoms include non-metallic elements such as N, P, etc., as well as metal elements such as Pt, Au, Fe, and Co.
  • nitrogen-doped graphene can even realize the transformation of its p-type and n-type semiconductors by adjusting the doping ratio of nitrogen, which has bright research prospects, so it is favored by researchers.
  • nitrogen-doped graphene is an electrode electrocatalyst material with excellent performance in oxygen reduction reaction (ORR) and oxygen evolution reaction (OER), graphene doped with a single nitrogen atom is not effective in hydrogen evolution reaction (HER).
  • ORR oxygen reduction reaction
  • OER oxygen evolution reaction
  • one of the improved strategies is to introduce metal atoms to construct multi-atom doped graphene catalysts, and in order to reduce the use of noble metal elements, more transition metal elements are used as alternative doping elements.
  • Fe element is a metal element with good activity and relatively low cost. At present, there is no report about nitrogen-doped graphene/carbon nanofiber axial composites loaded with single-atom iron for hydrogen production by hydrolysis.
  • the purpose of the present invention is to provide a preparation method of biomass-based nitrogen-doped graphene/nano-carbon fiber axial composite material loaded with monatomic iron.
  • Another object of the present invention is to provide the biomass-based nitrogen-doped graphene/nano-carbon fiber axial composite material loaded with monatomic iron prepared by the above method.
  • Another object of the present invention is to provide the application of the above product.
  • the purpose of the present invention is achieved by the following scheme: a preparation method of biomass-based nitrogen-doped graphene/nano-carbon fiber axial composite material loaded single-atom iron, first by precipitation method, the iron-containing compound is adsorbed on the biomass-based bacterial cellulose Surface; then introduce urea, pyrolyze the mixture of urea and iron salt-modified bacterial cellulose together at high temperature to obtain carbon nanofibers as veins, lamellar nitrogen-doped graphene coated on it, and the height of single-atom iron Composite materials, including the following steps:
  • the present invention proposes a preparation method of monoatomic iron/nitrogen-doped graphene and nano-carbon fiber axial composite material. Firstly, the iron-containing compound is adsorbed on the surface of biomass-based bacterial cellulose by precipitation method; then urea is introduced, and the The mixture of urea and iron salt-modified bacterial cellulose is pyrolyzed at high temperature to obtain a highly composite material with carbon nanofibers as the veins, lamellar nitrogen-doped graphene coated on it, and single-atom iron loaded at the same time.
  • the iron salt used in the process of loading iron metal nanoparticles is one of the raw materials of ferric chloride (or its hydrate) and ferric nitrate (or its hydrate).
  • the mass ratio of bacterial cellulose and urea used in the preparation process of iron salt-bacterial cellulose is preferably 1:20, and the concentration of the formed urea solution is not required, but it is necessary to ensure that the urea is completely dissolved and the solution can be completely dissolved. Submerge bacterial cellulose.
  • the holding temperature of the tube furnace is controlled above 800°C, preferably in the range of 900-1000°C.
  • the heating rate of the tube furnace is 3-10°C/min, preferably 5°C/min.
  • the present invention provides a kind of biomass-based nitrogen-doped graphene/nano-carbon fiber axial composite material loaded with monoatomic iron nanomaterials, which is prepared according to any of the above-mentioned methods, and the graphene in the axial composite material is The carbon fibers grow on both sides to form a coaxial composite structure.
  • the invention provides an application of an iron/nitrogen-doped graphene and nano-carbon fiber composite material as a catalyst material for electrocatalytic hydrolysis of hydrogen production.
  • the electrocatalytic effect of nitrogen-doped graphene composites on hydrogen evolution reaction (HER) is enhanced through the Mott-Schottky synergy of metal particles Fe and nitrogen atoms N.
  • the principle of the present invention is: firstly, the iron-containing compound is adsorbed on the surface of the biomass-based bacterial cellulose by precipitation method, and then calcined at high temperature under protective gas; Nitrogen-doped graphene, iron salt-bacterial cellulose chain polymers will be carbonized into single-atom iron-nano-carbon fiber materials, and finally through high-temperature pyrolysis of urea and iron salt-bacterial cellulose mixtures, nano-carbon fibers can be obtained. Veined, layered nitrogen-doped graphene is coated on it, and it is a highly composite nano-heterojunction material that supports iron single atoms. Due to the synergistic effect of metal particles and nitrogen atoms, the Mott-Schottky effect in the composite material is enhanced, which can improve the electrocatalytic effect of the nitrogen-doped composite carbon material on the hydrogen evolution reaction (HER).
  • HER hydrogen evolution reaction
  • the iron-containing compound is adsorbed on the surface of the biomass-based bacterial cellulose by a precipitation method.
  • nitrogen-doped graphene can be generated by heating and pyrolysis again, and the iron salt-bacterial cellulose chain is high
  • the molecules will be carbonized into single-atom iron-nano-carbon fiber materials, and through the high-temperature pyrolysis of urea and iron salt-bacterial cellulose mixture, the layer-like nitrogen-doped graphene coated with nano-carbon fibers as veins can be obtained.
  • the electrocatalytic effect of composite carbon materials on hydrogen evolution reaction (HER) is enhanced by the Mott-Schottky synergistic effect of metal particles Fe and nitrogen atoms N.
  • Fig. 1 is the transmission electron microscope (TEM) spectrogram of the synthetic iron/nitrogen-doped graphene/nano-carbon fiber axial composite material of embodiment 1 of the present invention
  • Fig. 2 is the polarization curve of the hydrogen evolution reaction catalyzed by the iron/nitrogen-doped graphene/carbon nanofiber axial composite material synthesized in Example 2 of the present invention.
  • a biomass-based nitrogen-doped graphene/nano-carbon fiber axial composite material supports single-atom iron.
  • the iron-containing compound is adsorbed on the surface of the biomass-based bacterial cellulose by precipitation; then urea is introduced, and the urea and iron salt
  • the modified bacterial cellulose mixture is pyrolyzed together at high temperature to obtain a highly composite material with carbon nanofibers as veins, lamellar nitrogen-doped graphene coated on it, and single-atom iron loaded at the same time. It is prepared according to the following steps:
  • the preparation of iron salt-bacterial cellulose rinse the bacterial cellulose film of 0.5g repeatedly with deionized water, then completely immerse the cleaned bacterial cellulose film in 300ml concentration of 0.1mol/L ferric nitrate solution, at the same time 4.0g of urea was dropped into the solution and fully stirred to completely dissolve the urea and the solution was completely immersed in the bacterial cellulose to obtain the iron salt-bacterial cellulose chain polymer compound supported by iron metal nanoparticles;
  • step b Preparation of nitrogen-doped graphene/carbon nanofiber axial nanocomposites loaded with monoatomic iron: the iron salt-bacterial cellulose chain polymer compound obtained in step a is completely frozen into a solid in a refrigerator, and then The frozen sample was placed in a freeze dryer for freeze-drying to obtain an aerogel of bacterial cellulose and white flocculent urea; finally, the resulting white aerogel was placed in a tube furnace and heated at a temperature of 5°C/min. Slowly heated to 900°C and held for 1 hour, cooled naturally to room temperature, and protected by high-purity N2 gas throughout the process, a black carbon airgel was obtained, which was nitrogen-doped graphene/carbon nanofibers loaded with monatomic iron. composite nanomaterials.
  • Fig. 1 is the transmission electron microscope (TEM) spectrogram of the iron/nitrogen-doped graphene/nano-carbon fiber axial composite material synthesized by the method of this embodiment, as can be seen from the figure, the loaded iron nanoparticles present a single particle shape, nitrogen-doped
  • the thickness of graphene is generally 0.34-13nm, and the thickness of carbon nanowires is 1-500nm.
  • the nitrogen-doped graphene/nano-carbon fiber axial nanocomposite material of 200 mg of the resulting product loaded with monoatomic iron as a working electrode, wash it with ethanol, and fix the electrode clamp;
  • the reference electrode is an Ag/AgCl electrode;
  • the counter electrode is a rotating Disc platinum electrode.
  • Fig. 2 is the polarization curve of the hydrogen evolution reaction of the iron/nitrogen-doped graphene/carbon nanofiber axial composite catalyst synthesized in the embodiment of the present invention.
  • the voltage scanning speed ranges from 5 to 25 mV/s. Under different scanning speeds, the catalyst has a high catalytic hydrogen production efficiency and a good hydrogen evolution rate.
  • a biomass-based nitrogen-doped graphene/carbon nanofiber axial composite material loaded with single-atom iron is similar to the steps in the examples, and is prepared according to the following steps:
  • step b Preparation of nitrogen-doped graphene/carbon nanofiber axial nanocomposites loaded with monoatomic iron: the iron salt-bacterial cellulose chain polymer compound obtained in step a is completely frozen into a solid in a refrigerator, and then The frozen sample was placed in a freeze dryer for freeze-drying to obtain an aerogel of bacterial cellulose and white flocculent urea; finally, the resulting white aerogel was placed in a tube furnace and heated at a temperature of 5°C/min. Slowly heated to 950°C and held for 1 hour, cooled naturally to room temperature, and protected by high-purity N2 gas throughout the process, a black carbon airgel was obtained, which was nitrogen-doped graphene/carbon nanofibers loaded with monatomic iron. composite nanomaterials.
  • a biomass-based nitrogen-doped graphene/carbon nanofiber axial composite material loaded with single-atom iron is similar to the steps in the examples, and is prepared according to the following steps:
  • the preparation of iron salt-bacterial cellulose rinse the bacterial cellulose film of 0.5g repeatedly with deionized water, then completely immerse the cleaned bacterial cellulose film in 300ml concentration of 0.1mol/L ferric nitrate solution, at the same time Put 4.0g of urea into the solution and stir fully to make the urea dissolve completely and the solution is completely submerged in the bacterial cellulose. After the immersion is complete, take out the bacterial cellulose film, which is the iron salt-bacterial cellulose chain polymer compound;
  • step b Preparation of nitrogen-doped graphene/carbon nanofiber axial nanocomposites loaded with monoatomic iron: the iron salt-bacterial cellulose chain polymer compound obtained in step a is completely frozen into a solid in a refrigerator, and then The frozen sample was placed in a freeze dryer for freeze-drying to obtain an aerogel of bacterial cellulose and white flocculent urea; finally, the resulting white aerogel was placed in a tube furnace and heated at a temperature of 5°C/min. Slowly heated to 1000°C and held for 1 hour, cooled naturally to room temperature, and protected by high-purity N2 gas throughout the process, a black carbon airgel was obtained, which was nitrogen-doped graphene/carbon nanofibers loaded with monatomic iron. composite nanomaterials.

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Abstract

Disclosed are a preparation method for a biomass-based nitrogen-doped graphene/nano carbon fiber axial composite material loaded with monatomic iron, and a product and use thereof. Firstly, an iron-containing compound is adsorbed on a surface of biomass-based bacterial cellulose by means of a precipitation method, and then is calcined at a high temperature under protective gas. Urea is subjected to thermal polycondensation to form carbon nitride in this process and then continues to be converted into nitrogen-doped graphene, an iron salt-bacterial cellulose chain-shaped polymer is carbonized into a monatomic iron-nano carbon fiber material, and finally by means of high-temperature pyrolysis of the urea and an iron salt-bacterial cellulose mixture, a highly composite nano heterojunction material which has nano carbon fibers as veins, has a layer of nitrogen-doped graphene coated on said fibers and, at the same time, is loaded with monatomic iron can be obtained. Due to the synergistic effect of metal particles and nitrogen atoms, the Mott-Scholtky effect present in the composite material is enhanced, so that the electrocatalytic effect of the nitrogen-doped composite carbon material on the hydrogen evolution reaction can be improved.

Description

生物质基氮掺杂石墨烯/纳米碳纤维轴向复合材料负载单原子铁的制备及产品和应用Preparation, product and application of biomass-based nitrogen-doped graphene/carbon nanofiber axial composites loaded with monoatomic iron 技术领域technical field
本发明属于纳米金属-半导体复合材料制备领域，具体涉及一种生物质基氮掺杂石墨烯/纳米碳纤维轴向复合材料负载单原子铁的制备方法及其产品和应用。The invention belongs to the field of preparation of nano metal-semiconductor composite materials, and in particular relates to a preparation method of biomass-based nitrogen-doped graphene/nano-carbon fiber axial composite material loaded with monoatomic iron and its product and application.
背景技术Background technique
氢气兼具了高能量密度优势和环境友好优势，是符合人类社会发展要求的重要清洁能源之一，有着十分广泛的应用前景。在以氢气作为能源载体并最终发挥其功效的一系列环节，如制氢、储氢及氢能量释放等环节中，制氢无疑是一个关键。目前工业制氢的主要方式是各种矿物燃料制氢，但是该过程会对环境造成污染。长远来看，因水解制氢的反应物与氢气释放能量后的产物一致，两个反应正好形成闭环，故水解制氢是最为环保且可循环的制氢方式。而在电催化水解制氢效果上最好的催化剂为贵金属Pt基催化剂，但丰度低，价格贵的因素亦制约了其广泛应用，所以寻找资源丰富、催化性能优异且持久的非贵金属催化剂是未来氢能源开发利用的关键。Hydrogen has both the advantages of high energy density and environmental friendliness. It is one of the important clean energy that meets the development requirements of human society and has a very broad application prospect. In a series of links that use hydrogen as an energy carrier and finally exert its efficacy, such as hydrogen production, hydrogen storage and hydrogen energy release, hydrogen production is undoubtedly a key. At present, the main way of industrial hydrogen production is hydrogen production from various fossil fuels, but this process will pollute the environment. In the long run, because the reactants of hydrogen production by hydrolysis are the same as the products after hydrogen releases energy, the two reactions just form a closed loop, so hydrogen production by hydrolysis is the most environmentally friendly and recyclable hydrogen production method. The catalyst with the best electrocatalytic hydrolysis hydrogen production effect is the noble metal Pt-based catalyst, but its low abundance and high price also restrict its wide application. The key to the development and utilization of hydrogen energy in the future.
近年来，石墨烯因其高的比表面积、优异的电性能、丰富的活性位点和不俗的稳定性而成为光电催化化学应用中的重点研究对象。除这些优点外，人们通过对石墨烯材料的改性以调变电子结构，可以增强其对催化反应物的选择性、催化性能或是兼而有之，而形貌调控和杂原子掺杂等改性方法就是目前应用最为广泛的调节石墨烯性能的手段。杂原子掺杂的改性方法常用的掺杂原子有诸如N、P等之类的非金属元素，也有Pt、Au、Fe、Co等金属元素。其中，氮掺杂石墨烯甚至可以通过调整氮元素的掺杂比例而实现其p型和n型半导体的转变，有着亮眼的研究前景，故深受研究人员的青睐。In recent years, graphene has become a key research object in the application of photocatalytic chemistry due to its high specific surface area, excellent electrical properties, abundant active sites and good stability. In addition to these advantages, by modifying the electronic structure of graphene materials, people can enhance their selectivity to catalytic reactants, catalytic performance or both, and morphology control and heteroatom doping, etc. The modification method is currently the most widely used means to adjust the properties of graphene. The modification method of heteroatom doping The commonly used doping atoms include non-metallic elements such as N, P, etc., as well as metal elements such as Pt, Au, Fe, and Co. Among them, nitrogen-doped graphene can even realize the transformation of its p-type and n-type semiconductors by adjusting the doping ratio of nitrogen, which has bright research prospects, so it is favored by researchers.
以往的研究表明，虽然氮掺杂石墨烯是性能优异的氧还原反应(ORR)和氧析出反应(OER)电极电催化材料，但是氮原子单一掺杂的石墨烯在氢析出反应(HER)上的表现却是平平。对此，改进的策略之一是引入金属原子，从而构建多原子掺杂的石墨烯催化剂，且为了减少贵金属元素的使用，多采用过渡金属元素作为替代的掺杂元素。Fe元素属于活性良好且成本相对较低的金属元素，目前没有关于氮掺杂石墨烯/纳米碳纤维轴向复合材料负载单原子铁应用于水解制氢的报道。Previous studies have shown that although nitrogen-doped graphene is an electrode electrocatalyst material with excellent performance in oxygen reduction reaction (ORR) and oxygen evolution reaction (OER), graphene doped with a single nitrogen atom is not effective in hydrogen evolution reaction (HER). The performance is mediocre. In this regard, one of the improved strategies is to introduce metal atoms to construct multi-atom doped graphene catalysts, and in order to reduce the use of noble metal elements, more transition metal elements are used as alternative doping elements. Fe element is a metal element with good activity and relatively low cost. At present, there is no report about nitrogen-doped graphene/carbon nanofiber axial composites loaded with single-atom iron for hydrogen production by hydrolysis.
发明内容Contents of the invention
为克服现有技术的不足，本发明目的在于提供一种生物质基氮掺杂石墨烯/纳米碳纤维轴向复合材料负载单原子铁的制备方法。In order to overcome the deficiencies of the prior art, the purpose of the present invention is to provide a preparation method of biomass-based nitrogen-doped graphene/nano-carbon fiber axial composite material loaded with monatomic iron.
本发明的再一目的在于：提供上述方法制备的生物质基氮掺杂石墨烯/纳米碳纤维轴向复合材料负载单原子铁产品。Another object of the present invention is to provide the biomass-based nitrogen-doped graphene/nano-carbon fiber axial composite material loaded with monatomic iron prepared by the above method.
本发明的又一目的在于：提供上述产品的应用。Another object of the present invention is to provide the application of the above product.
本发明目的通过以下方案实现：一种生物质基氮掺杂石墨烯/纳米碳纤维轴向复合材料负载单原子铁的制备方法，先通过沉淀法将含铁化合物吸附在生物质基细菌纤维素的表面；接着引入尿素，将尿素和铁盐改性的细菌纤维素混合物一起高温热解得到以纳米碳纤维为脉络，层片状氮掺杂石墨烯包覆其上，同时负载单原子的铁的高度复合材料，包括以下步骤：The purpose of the present invention is achieved by the following scheme: a preparation method of biomass-based nitrogen-doped graphene/nano-carbon fiber axial composite material loaded single-atom iron, first by precipitation method, the iron-containing compound is adsorbed on the biomass-based bacterial cellulose Surface; then introduce urea, pyrolyze the mixture of urea and iron salt-modified bacterial cellulose together at high temperature to obtain carbon nanofibers as veins, lamellar nitrogen-doped graphene coated on it, and the height of single-atom iron Composite materials, including the following steps:
a、铁盐-细菌纤维素的制备：用去离子水反复冲洗一定质量的细菌纤维素薄膜，之后将清洗干净的细菌纤维素薄膜完全浸入0.1mol/L的铁盐溶液中，同时，投入尿素，使细菌纤维素与尿素质量比为1:1～1:40之间，搅拌24小时，使尿素完全溶解且溶液完全浸没细菌纤维素，得到铁金属纳米粒子负载的铁盐-细菌纤维素链状高分子化合物；a. Preparation of iron salt-bacterial cellulose: Rinse a certain quality of bacterial cellulose film repeatedly with deionized water, then completely immerse the cleaned bacterial cellulose film in 0.1mol/L iron salt solution, and at the same time, put in urea , so that the mass ratio of bacterial cellulose to urea is between 1:1 and 1:40, and stirred for 24 hours, the urea is completely dissolved and the solution is completely submerged in bacterial cellulose to obtain iron salt-bacterial cellulose chains supported by iron metal nanoparticles shape polymer compound;
b、负载单原子铁的氮掺杂石墨烯/纳米碳纤维轴向纳米复合材料的制备：将步骤a中得到的铁盐-细菌纤维素链状高分子化合物进行冷冻干燥，便得到细菌纤维素与白色絮状尿素的气凝胶；将所得气凝胶置于管式炉中，加热至不低于800℃高温并保温1小时，自然冷却至室温，全程通N 2气保护，得到黑色的碳气凝胶，即为负载单原子铁的氮掺杂石墨烯/纳米碳纤维轴向复合纳米材料。 b. Preparation of nitrogen-doped graphene/carbon nanofiber axial nanocomposites loaded with monoatomic iron: freeze-dry the iron salt-bacterial cellulose chain polymer compound obtained in step a to obtain bacterial cellulose and Airgel of white flocculent urea; put the obtained airgel in a tube furnace, heat it to a high temperature of not lower than 800°C and keep it warm for 1 hour, cool it naturally to room temperature, and pass N2 gas protection throughout the process to obtain black carbon Airgel is a nitrogen-doped graphene/carbon nanofiber axial composite nanomaterial loaded with monoatomic iron.
本发明提出了一种单原子铁/氮掺杂石墨烯与纳米碳纤维轴向复合材料的制备方法，首先通过沉淀法将含铁化合物吸附在生物质基细菌纤维素的表面；接着引入尿素，将尿素和铁盐改性的细菌纤维素混合物一起高温热解便获得了以纳米碳纤维为脉络，层片状氮掺杂石墨烯包覆其上，同时负载单原子的铁的高度复合材料。The present invention proposes a preparation method of monoatomic iron/nitrogen-doped graphene and nano-carbon fiber axial composite material. Firstly, the iron-containing compound is adsorbed on the surface of biomass-based bacterial cellulose by precipitation method; then urea is introduced, and the The mixture of urea and iron salt-modified bacterial cellulose is pyrolyzed at high temperature to obtain a highly composite material with carbon nanofibers as the veins, lamellar nitrogen-doped graphene coated on it, and single-atom iron loaded at the same time.
步骤a中，所述的铁金属纳米粒子负载的过程中所用的铁盐为氯化铁(或其水合物)、硝酸铁(或其水合物)原料中的一种。In step a, the iron salt used in the process of loading iron metal nanoparticles is one of the raw materials of ferric chloride (or its hydrate) and ferric nitrate (or its hydrate).
步骤a中，铁盐-细菌纤维素的制备过程中所用的细菌纤维素与尿素质量比以1:20为优选，所形成的尿素溶液浓度不做要求，但需保证尿素完全溶解且溶液能完全浸没细菌纤维素。In step a, the mass ratio of bacterial cellulose and urea used in the preparation process of iron salt-bacterial cellulose is preferably 1:20, and the concentration of the formed urea solution is not required, but it is necessary to ensure that the urea is completely dissolved and the solution can be completely dissolved. Submerge bacterial cellulose.
所述的管式炉保温温度控制在800℃以上，以900～1000℃区间范围为优选。The holding temperature of the tube furnace is controlled above 800°C, preferably in the range of 900-1000°C.
所述的管式炉加热速率为3～10℃/min，以5℃/min为优选。The heating rate of the tube furnace is 3-10°C/min, preferably 5°C/min.
本发明提供一种生物质基氮掺杂石墨烯/纳米碳纤维轴向复合材料负载单原子铁的 纳米材料，根据上述任一所述方法制备得到的，所述的轴向复合材料中石墨烯沿碳纤维两侧生长，形成同轴复合结构。The present invention provides a kind of biomass-based nitrogen-doped graphene/nano-carbon fiber axial composite material loaded with monoatomic iron nanomaterials, which is prepared according to any of the above-mentioned methods, and the graphene in the axial composite material is The carbon fibers grow on both sides to form a coaxial composite structure.
本发明提供一种铁/氮掺杂石墨烯与纳米碳纤维复合材料作为电催化水解制氢的催化剂材料的应用。通过金属粒子Fe与氮原子N的Mott-Schottky协同作用，增强了氮掺杂石墨烯复合材料在氢析出反应(HER)上的电催化效果。The invention provides an application of an iron/nitrogen-doped graphene and nano-carbon fiber composite material as a catalyst material for electrocatalytic hydrolysis of hydrogen production. The electrocatalytic effect of nitrogen-doped graphene composites on hydrogen evolution reaction (HER) is enhanced through the Mott-Schottky synergy of metal particles Fe and nitrogen atoms N.
本发明原理是：首先通过沉淀法将含铁化合物吸附在生物质基细菌纤维素的表面，接着在保护性气体下于高温煅烧；尿素在此过程会热缩聚为氮化碳后再继续转化为氮掺杂石墨烯，铁盐-细菌纤维素链状高分子则会碳化为单原子铁-纳米碳纤维材料，最终通过对尿素和铁盐-细菌纤维素混合物的高温热解可以获得以纳米碳纤维为脉络、层状氮掺杂石墨烯包覆其上，同时负载铁单原子的高度复合的纳米异质结材料。由于金属粒子与氮原子的协同作用，导致了该复合材料中存在的Mott-Schottky效应增强，因而可提高氮掺杂的复合碳材料在氢析出反应(HER)上的电催化效果。The principle of the present invention is: firstly, the iron-containing compound is adsorbed on the surface of the biomass-based bacterial cellulose by precipitation method, and then calcined at high temperature under protective gas; Nitrogen-doped graphene, iron salt-bacterial cellulose chain polymers will be carbonized into single-atom iron-nano-carbon fiber materials, and finally through high-temperature pyrolysis of urea and iron salt-bacterial cellulose mixtures, nano-carbon fibers can be obtained. Veined, layered nitrogen-doped graphene is coated on it, and it is a highly composite nano-heterojunction material that supports iron single atoms. Due to the synergistic effect of metal particles and nitrogen atoms, the Mott-Schottky effect in the composite material is enhanced, which can improve the electrocatalytic effect of the nitrogen-doped composite carbon material on the hydrogen evolution reaction (HER).
本发明通过沉淀法将含铁化合物吸附在生物质基细菌纤维素的表面，基于尿素热缩聚为氮化碳后再度升温热解可生成氮掺杂石墨烯，铁盐-细菌纤维素链状高分子经煅烧会碳化为单原子铁-纳米碳纤维材料，通过对尿素和铁盐-细菌纤维素混合物的高温热解便获得以纳米碳纤维为脉络、层片状氮掺杂石墨烯包覆其上，同时负载单原子的铁的高度复合材料。通过金属粒子Fe与氮原子N的Mott-Schottky协同作用，增强了复合碳材料在氢析出反应(HER)上的电催化效果。In the present invention, the iron-containing compound is adsorbed on the surface of the biomass-based bacterial cellulose by a precipitation method. Based on the thermal condensation of urea into carbon nitride, nitrogen-doped graphene can be generated by heating and pyrolysis again, and the iron salt-bacterial cellulose chain is high After calcination, the molecules will be carbonized into single-atom iron-nano-carbon fiber materials, and through the high-temperature pyrolysis of urea and iron salt-bacterial cellulose mixture, the layer-like nitrogen-doped graphene coated with nano-carbon fibers as veins can be obtained. A highly composite material of iron supporting single atoms at the same time. The electrocatalytic effect of composite carbon materials on hydrogen evolution reaction (HER) is enhanced by the Mott-Schottky synergistic effect of metal particles Fe and nitrogen atoms N.
附图说明Description of drawings
图1为本发明实施例1合成的铁/氮掺杂石墨烯/纳米碳纤维轴向复合材料的透射电镜(TEM)谱图；Fig. 1 is the transmission electron microscope (TEM) spectrogram of the synthetic iron/nitrogen-doped graphene/nano-carbon fiber axial composite material of embodiment 1 of the present invention;
图2为本发明实施例2合成的铁/氮掺杂石墨烯/纳米碳纤维轴向复合材料催化氢析出反应的极化曲线。Fig. 2 is the polarization curve of the hydrogen evolution reaction catalyzed by the iron/nitrogen-doped graphene/carbon nanofiber axial composite material synthesized in Example 2 of the present invention.
具体实施方式Detailed ways
本实施例在以本发明技术方案为前提下进行实施，给出了详细的实施方式和具体的操作过程，但本发明的保护范围不限于下述的实施例。This embodiment is carried out on the premise of the technical solution of the present invention, and the detailed implementation and specific operation process are given, but the protection scope of the present invention is not limited to the following embodiments.
实施例1Example 1
一种生物质基氮掺杂石墨烯/纳米碳纤维轴向复合材料负载单原子铁，先通过沉淀法将含铁化合物吸附在生物质基细菌纤维素的表面；接着引入尿素，将尿素和铁盐改性的 细菌纤维素混合物一起高温热解得到以纳米碳纤维为脉络，层片状氮掺杂石墨烯包覆其上，同时负载单原子的铁的高度复合材料，按以下步骤制备：A biomass-based nitrogen-doped graphene/nano-carbon fiber axial composite material supports single-atom iron. First, the iron-containing compound is adsorbed on the surface of the biomass-based bacterial cellulose by precipitation; then urea is introduced, and the urea and iron salt The modified bacterial cellulose mixture is pyrolyzed together at high temperature to obtain a highly composite material with carbon nanofibers as veins, lamellar nitrogen-doped graphene coated on it, and single-atom iron loaded at the same time. It is prepared according to the following steps:
a、铁盐-细菌纤维素的制备：用去离子水反复冲洗0.5g的细菌纤维素薄膜，之后将清洗干净的细菌纤维素薄膜完全浸入300ml浓度为0.1mol/L的硝酸铁溶液中，同时向该溶液中投入4.0g尿素并充分搅拌，使尿素完全溶解且溶液完全浸没细菌纤维素，得到铁金属纳米粒子负载的铁盐-细菌纤维素链状高分子化合物；a, the preparation of iron salt-bacterial cellulose: rinse the bacterial cellulose film of 0.5g repeatedly with deionized water, then completely immerse the cleaned bacterial cellulose film in 300ml concentration of 0.1mol/L ferric nitrate solution, at the same time 4.0g of urea was dropped into the solution and fully stirred to completely dissolve the urea and the solution was completely immersed in the bacterial cellulose to obtain the iron salt-bacterial cellulose chain polymer compound supported by iron metal nanoparticles;
b、负载单原子铁的氮掺杂石墨烯/纳米碳纤维轴向纳米复合材料的制备：将步骤a中得到的铁盐-细菌纤维素链状高分子化合物置于冰箱中完全冷冻成固体，接着对冻结后的样品置于冷冻干燥机中进行冷冻干燥，得到细菌纤维素与白色絮状尿素的气凝胶；最后，将所得白色气凝胶置于管式炉中，以5℃/min的速率缓慢加热至900℃并保温1小时，自然冷却至室温，全程通高纯N 2气保护，得到黑色的碳气凝胶，即为负载单原子铁的氮掺杂石墨烯/纳米碳纤维轴向复合纳米材料。 b. Preparation of nitrogen-doped graphene/carbon nanofiber axial nanocomposites loaded with monoatomic iron: the iron salt-bacterial cellulose chain polymer compound obtained in step a is completely frozen into a solid in a refrigerator, and then The frozen sample was placed in a freeze dryer for freeze-drying to obtain an aerogel of bacterial cellulose and white flocculent urea; finally, the resulting white aerogel was placed in a tube furnace and heated at a temperature of 5°C/min. Slowly heated to 900°C and held for 1 hour, cooled naturally to room temperature, and protected by high-purity N2 gas throughout the process, a black carbon airgel was obtained, which was nitrogen-doped graphene/carbon nanofibers loaded with monatomic iron. composite nanomaterials.
经测定，该条件下得到的是负载量为4.7wt％铁单原子的氮掺杂石墨烯/纳米碳纤维轴向复合纳米材料。It has been determined that under this condition, a nitrogen-doped graphene/carbon nanofiber axial composite nanomaterial with a loading capacity of 4.7 wt% iron single atoms is obtained.
图1为本实施例方法合成的铁/氮掺杂石墨烯/纳米碳纤维轴向复合材料的透射电镜(TEM)谱图，由图可见，所负载的铁纳米粒子呈现单颗粒状，氮掺杂的石墨烯厚度一般为0.34～13nm，碳纳米线粗细为1～500nm。Fig. 1 is the transmission electron microscope (TEM) spectrogram of the iron/nitrogen-doped graphene/nano-carbon fiber axial composite material synthesized by the method of this embodiment, as can be seen from the figure, the loaded iron nanoparticles present a single particle shape, nitrogen-doped The thickness of graphene is generally 0.34-13nm, and the thickness of carbon nanowires is 1-500nm.
称取200mg的所得产品负载单原子铁的氮掺杂石墨烯/纳米碳纤维轴向纳米复合材料作为工作电极，用乙醇洗涤干净，电极夹固定；参比电极为Ag/AgCl电极；对电极为旋转圆盘铂电极。Take the nitrogen-doped graphene/nano-carbon fiber axial nanocomposite material of 200 mg of the resulting product loaded with monoatomic iron as a working electrode, wash it with ethanol, and fix the electrode clamp; the reference electrode is an Ag/AgCl electrode; the counter electrode is a rotating Disc platinum electrode.
图2为本发明实施例合成的铁/氮掺杂石墨烯/纳米碳纤维轴向复合催化剂氢析出反应的极化曲线。电压扫描速度范围为5～25mV/s，在不同的扫描速率下，该催化剂具有较高的催化制氢效率，并且呈现出较好的析氢倍率。Fig. 2 is the polarization curve of the hydrogen evolution reaction of the iron/nitrogen-doped graphene/carbon nanofiber axial composite catalyst synthesized in the embodiment of the present invention. The voltage scanning speed ranges from 5 to 25 mV/s. Under different scanning speeds, the catalyst has a high catalytic hydrogen production efficiency and a good hydrogen evolution rate.
实施例2Example 2
一种生物质基氮掺杂石墨烯/纳米碳纤维轴向复合材料负载单原子铁，与实施例步骤近似，按以下步骤制备：A biomass-based nitrogen-doped graphene/carbon nanofiber axial composite material loaded with single-atom iron is similar to the steps in the examples, and is prepared according to the following steps:
a、铁盐-细菌纤维素的制备：用去离子水反复冲洗0.5g的细菌纤维素薄膜，之后将清洗干净的细菌纤维素薄膜完全浸入300ml浓度为0.1mol/L的三氯化铁溶液中，同时向该溶液中投入4.0g尿素并充分搅拌，使尿素完全溶解且溶液完全浸没细菌纤维素，待浸 入完全后取出细菌纤维素薄膜，即为铁盐-细菌纤维素链状高分子化合物；a. Preparation of iron salt-bacterial cellulose: rinse 0.5g of bacterial cellulose film repeatedly with deionized water, then completely immerse the cleaned bacterial cellulose film in 300ml ferric chloride solution with a concentration of 0.1mol/L At the same time, 4.0g of urea is dropped into the solution and fully stirred to completely dissolve the urea and completely submerge the bacterial cellulose in the solution. After the immersion is complete, the bacterial cellulose film is taken out, which is the iron salt-bacterial cellulose chain polymer compound;
b、负载单原子铁的氮掺杂石墨烯/纳米碳纤维轴向纳米复合材料的制备：将步骤a中得到的铁盐-细菌纤维素链状高分子化合物置于冰箱中完全冷冻成固体，接着对冻结后的样品置于冷冻干燥机中进行冷冻干燥，得到细菌纤维素与白色絮状尿素的气凝胶；最后，将所得白色气凝胶置于管式炉中，以5℃/min的速率缓慢加热至950℃并保温1小时，自然冷却至室温，全程通高纯N 2气保护，得到黑色的碳气凝胶，即为负载单原子铁的氮掺杂石墨烯/纳米碳纤维轴向复合纳米材料。 b. Preparation of nitrogen-doped graphene/carbon nanofiber axial nanocomposites loaded with monoatomic iron: the iron salt-bacterial cellulose chain polymer compound obtained in step a is completely frozen into a solid in a refrigerator, and then The frozen sample was placed in a freeze dryer for freeze-drying to obtain an aerogel of bacterial cellulose and white flocculent urea; finally, the resulting white aerogel was placed in a tube furnace and heated at a temperature of 5°C/min. Slowly heated to 950°C and held for 1 hour, cooled naturally to room temperature, and protected by high-purity N2 gas throughout the process, a black carbon airgel was obtained, which was nitrogen-doped graphene/carbon nanofibers loaded with monatomic iron. composite nanomaterials.
经测定，该条件下得到的是负载量为6.3wt％铁单原子的氮掺杂石墨烯/纳米碳纤维轴向复合纳米材料。It has been determined that under this condition, a nitrogen-doped graphene/carbon nanofiber axial composite nanomaterial with a loading capacity of 6.3 wt% iron single atoms is obtained.
实施例3Example 3
一种生物质基氮掺杂石墨烯/纳米碳纤维轴向复合材料负载单原子铁，与实施例步骤近似，按以下步骤制备：A biomass-based nitrogen-doped graphene/carbon nanofiber axial composite material loaded with single-atom iron is similar to the steps in the examples, and is prepared according to the following steps:
a、铁盐-细菌纤维素的制备：用去离子水反复冲洗0.5g的细菌纤维素薄膜，之后将清洗干净的细菌纤维素薄膜完全浸入300ml浓度为0.1mol/L的硝酸铁溶液中，同时向该溶液中投入4.0g尿素并充分搅拌，使尿素完全溶解且溶液完全浸没细菌纤维素，待浸入完全后取出细菌纤维素薄膜，即为铁盐-细菌纤维素链状高分子化合物；a, the preparation of iron salt-bacterial cellulose: rinse the bacterial cellulose film of 0.5g repeatedly with deionized water, then completely immerse the cleaned bacterial cellulose film in 300ml concentration of 0.1mol/L ferric nitrate solution, at the same time Put 4.0g of urea into the solution and stir fully to make the urea dissolve completely and the solution is completely submerged in the bacterial cellulose. After the immersion is complete, take out the bacterial cellulose film, which is the iron salt-bacterial cellulose chain polymer compound;
b、负载单原子铁的氮掺杂石墨烯/纳米碳纤维轴向纳米复合材料的制备：将步骤a中得到的铁盐-细菌纤维素链状高分子化合物置于冰箱中完全冷冻成固体，接着对冻结后的样品置于冷冻干燥机中进行冷冻干燥，得到细菌纤维素与白色絮状尿素的气凝胶；最后，将所得白色气凝胶置于管式炉中，以5℃/min的速率缓慢加热至1000℃并保温1小时，自然冷却至室温，全程通高纯N 2气保护，得到黑色的碳气凝胶，即为负载单原子铁的氮掺杂石墨烯/纳米碳纤维轴向复合纳米材料。 b. Preparation of nitrogen-doped graphene/carbon nanofiber axial nanocomposites loaded with monoatomic iron: the iron salt-bacterial cellulose chain polymer compound obtained in step a is completely frozen into a solid in a refrigerator, and then The frozen sample was placed in a freeze dryer for freeze-drying to obtain an aerogel of bacterial cellulose and white flocculent urea; finally, the resulting white aerogel was placed in a tube furnace and heated at a temperature of 5°C/min. Slowly heated to 1000°C and held for 1 hour, cooled naturally to room temperature, and protected by high-purity N2 gas throughout the process, a black carbon airgel was obtained, which was nitrogen-doped graphene/carbon nanofibers loaded with monatomic iron. composite nanomaterials.
经测定，该条件下得到的是负载量为8.1wt％铁单原子的氮掺杂石墨烯/纳米碳纤维轴向复合纳米材料。It has been determined that under this condition, a nitrogen-doped graphene/carbon nanofiber axial composite nanomaterial with a loading capacity of 8.1 wt% iron single atoms is obtained.
以上所述仅为本发明的较佳实施例而已，并不用以限制本发明，凡在本发明的精神和原则之内所作的任何修改、等同替换和改进等，均应包含在本发明的保护范围之内。The above descriptions are only preferred embodiments of the present invention, and are not intended to limit the present invention. Any modifications, equivalent replacements and improvements made within the spirit and principles of the present invention should be included in the protection of the present invention. within range.

Claims (10)

  1. 一种生物质基氮掺杂石墨烯/纳米碳纤维轴向复合材料负载单原子铁的制备方法，先通过沉淀法将含铁化合物吸附在生物质基细菌纤维素的表面；接着引入尿素，将尿素和铁盐改性的细菌纤维素混合物一起高温热解得到以纳米碳纤维为脉络，层片状氮掺杂石墨烯包覆其上，同时负载单原子的铁的高度复合材料，其特征在于，包括以下步骤：A preparation method of biomass-based nitrogen-doped graphene/nano-carbon fiber axial composite material loaded with monoatomic iron. First, the iron-containing compound is adsorbed on the surface of biomass-based bacterial cellulose by precipitation; then urea is introduced, and the urea High-temperature pyrolysis with the bacterial cellulose mixture modified by iron salts to obtain a highly composite material with nano-carbon fibers as veins, lamellar nitrogen-doped graphene coated on it, and single-atom iron loaded at the same time, characterized in that it includes The following steps:
    a、铁盐-细菌纤维素的制备：用去离子水反复冲洗一定质量的细菌纤维素薄膜，之后将清洗干净的细菌纤维素薄膜完全浸入0.1mol/L的铁盐溶液中，同时，投入尿素，使细菌纤维素与尿素质量比为1:1～1:40之间，充分搅拌，使尿素完全溶解且溶液完全浸没细菌纤维素，得到铁金属纳米粒子负载的铁盐-细菌纤维素链状高分子化合物；a. Preparation of iron salt-bacterial cellulose: Rinse a certain quality of bacterial cellulose film repeatedly with deionized water, then completely immerse the cleaned bacterial cellulose film in 0.1mol/L iron salt solution, and at the same time, put in urea , so that the mass ratio of bacterial cellulose to urea is between 1:1 and 1:40, fully stirred, the urea is completely dissolved and the solution is completely immersed in the bacterial cellulose, and the iron salt-bacterial cellulose chain supported by iron metal nanoparticles is obtained. polymer compound;
    b、负载单原子铁的氮掺杂石墨烯/纳米碳纤维轴向纳米复合材料的制备：将步骤a中得到的铁盐-细菌纤维素链状高分子化合物进行冷冻干燥，便得到细菌纤维素与白色絮状尿素的气凝胶；将所得气凝胶置于管式炉中，加热至不低于800℃高温并保温1小时，自然冷却至室温，全程通N 2气保护，得到黑色的碳气凝胶，即为负载单原子铁的氮掺杂石墨烯/纳米碳纤维轴向复合纳米材料。 b. Preparation of nitrogen-doped graphene/carbon nanofiber axial nanocomposites loaded with monoatomic iron: freeze-dry the iron salt-bacterial cellulose chain polymer compound obtained in step a to obtain bacterial cellulose and Airgel of white flocculent urea; put the obtained airgel in a tube furnace, heat it to a high temperature of not lower than 800°C and keep it warm for 1 hour, cool it naturally to room temperature, and pass N2 gas protection throughout the process to obtain black carbon Airgel is a nitrogen-doped graphene/carbon nanofiber axial composite nanomaterial loaded with monoatomic iron.
  2. 根据权利要求1所述的一种生物质基氮掺杂石墨烯/纳米碳纤维轴向复合材料负载单原子铁的制备方法，其特征在于，步骤a中，所用的铁盐为氯化铁或其水合物、硝酸铁或其水合物中的一种。The preparation method of a kind of biomass-based nitrogen-doped graphene/carbon nanofiber axial composite material supporting monatomic iron according to claim 1, characterized in that, in step a, the iron salt used is ferric chloride or its Hydrate, ferric nitrate or one of its hydrates.
  3. 根据权利要求1所述的一种生物质基氮掺杂石墨烯/纳米碳纤维轴向复合材料负载单原子铁的制备方法，其特征在于，步骤a中，铁盐-细菌纤维素的制备过程中所用的细菌纤维素与尿素质量比为1:20。The preparation method of a kind of biomass-based nitrogen-doped graphene/carbon nanofiber axial composite material supporting monatomic iron according to claim 1, characterized in that, in step a, during the preparation of iron salt-bacterial cellulose The mass ratio of bacterial cellulose to urea used was 1:20.
  4. 根据权利要求1所述的一种生物质基氮掺杂石墨烯/纳米碳纤维轴向复合材料负载单原子铁的制备方法，其特征在于，所述的管式炉保温温度控制在900～1000℃区间范围。The preparation method of a biomass-based nitrogen-doped graphene/carbon nanofiber axial composite material loaded with monatomic iron according to claim 1, characterized in that the holding temperature of the tube furnace is controlled at 900-1000°C Interval range.
  5. 根据权利要求1所述的一种生物质基氮掺杂石墨烯/纳米碳纤维轴向复合材料负载单原子铁的制备方法，其特征在于，所述的管式炉加热速率为3～10℃/min。The preparation method of a biomass-based nitrogen-doped graphene/carbon nanofiber axial composite material supporting monoatomic iron according to claim 1, characterized in that, the heating rate of the tube furnace is 3-10 °C/ min.
  6. 根据权利要求1至5任一项所述的一种生物质基氮掺杂石墨烯/纳米碳纤维轴向复合材料负载单原子铁的制备方法，其特征在于，按以下步骤制备：The preparation method of a kind of biomass-based nitrogen-doped graphene/carbon nanofiber axial composite material supporting monatomic iron according to any one of claims 1 to 5, characterized in that, it is prepared according to the following steps:
    a、铁盐-细菌纤维素的制备：用去离子水反复冲洗0.5g的细菌纤维素薄膜，之后将清洗干净的细菌纤维素薄膜完全浸入300ml浓度为0.1mol/L的硝酸铁溶液中，同时向该溶液中投入4.0g尿素并充分搅拌，使尿素完全溶解且溶液完全浸没细菌纤维素，得到铁金属纳米粒子负载的铁盐-细菌纤维素链状高分子化合物；a, the preparation of iron salt-bacterial cellulose: rinse the bacterial cellulose film of 0.5g repeatedly with deionized water, then completely immerse the cleaned bacterial cellulose film in 300ml concentration of 0.1mol/L ferric nitrate solution, at the same time 4.0g of urea was dropped into the solution and fully stirred to completely dissolve the urea and the solution was completely immersed in the bacterial cellulose to obtain the iron salt-bacterial cellulose chain polymer compound supported by iron metal nanoparticles;
    b、负载单原子铁的氮掺杂石墨烯/纳米碳纤维轴向纳米复合材料的制备：将步骤a中得到的铁盐-细菌纤维素链状高分子化合物置于冰箱中完全冷冻成固体，接着对冻结后的样品置于冷冻干燥机中进行冷冻干燥，得到细菌纤维素与白色絮状尿素的气凝胶；最后，将所得白色气凝胶置于管式炉中，以5℃/min的速率缓慢加热至900℃并保温1小时，自然冷却至室温，全程通高纯N 2气保护，得到黑色的碳气凝胶，即为负载单原子铁的氮掺杂石墨烯/纳米碳纤维轴向复合纳米材料。 b. Preparation of nitrogen-doped graphene/carbon nanofiber axial nanocomposites loaded with monoatomic iron: the iron salt-bacterial cellulose chain polymer compound obtained in step a is completely frozen into a solid in a refrigerator, and then The frozen sample was placed in a freeze dryer for freeze-drying to obtain an aerogel of bacterial cellulose and white flocculent urea; finally, the resulting white aerogel was placed in a tube furnace and heated at a temperature of 5°C/min. Slowly heated to 900°C and held for 1 hour, cooled naturally to room temperature, and protected by high-purity N2 gas throughout the process, a black carbon airgel was obtained, which was nitrogen-doped graphene/carbon nanofibers loaded with monatomic iron. composite nanomaterials.
  7. 根据权利要求1至5任一项所述的一种生物质基氮掺杂石墨烯/纳米碳纤维轴向复合材料负载单原子铁的制备方法，其特征在于，按以下步骤制备：The preparation method of a kind of biomass-based nitrogen-doped graphene/carbon nanofiber axial composite material supporting monatomic iron according to any one of claims 1 to 5, characterized in that, it is prepared according to the following steps:
    a、铁盐-细菌纤维素的制备：用去离子水反复冲洗0.5g的细菌纤维素薄膜，之后将清洗干净的细菌纤维素薄膜完全浸入300ml浓度为0.1mol/L的三氯化铁溶液中，同时向该溶液中投入4.0g尿素并充分搅拌，使尿素完全溶解且溶液完全浸没细菌纤维素，待浸入完全后取出细菌纤维素薄膜，即为铁盐-细菌纤维素链状高分子化合物；a. Preparation of iron salt-bacterial cellulose: rinse 0.5g of bacterial cellulose film repeatedly with deionized water, then completely immerse the cleaned bacterial cellulose film in 300ml ferric chloride solution with a concentration of 0.1mol/L At the same time, 4.0g of urea is dropped into the solution and fully stirred to completely dissolve the urea and completely submerge the bacterial cellulose in the solution. After the immersion is complete, the bacterial cellulose film is taken out, which is the iron salt-bacterial cellulose chain polymer compound;
    b、负载单原子铁的氮掺杂石墨烯/纳米碳纤维轴向纳米复合材料的制备：将步骤a中得到的铁盐-细菌纤维素链状高分子化合物置于冰箱中完全冷冻成固体，接着对冻结后的样品置于冷冻干燥机中进行冷冻干燥，得到细菌纤维素与白色絮状尿素的气凝胶；最后，将所得白色气凝胶置于管式炉中，以5℃/min的速率缓慢加热至950℃并保温1小时，自然冷却至室温，全程通高纯N 2气保护，得到黑色的碳气凝胶，即为负载单原子铁的氮掺杂石墨烯/纳米碳纤维轴向复合纳米材料。 b. Preparation of nitrogen-doped graphene/carbon nanofiber axial nanocomposites loaded with monoatomic iron: the iron salt-bacterial cellulose chain polymer compound obtained in step a is completely frozen into a solid in a refrigerator, and then The frozen sample was placed in a freeze dryer for freeze-drying to obtain an aerogel of bacterial cellulose and white flocculent urea; finally, the resulting white aerogel was placed in a tube furnace and heated at a temperature of 5°C/min. Slowly heated to 950°C and held for 1 hour, cooled naturally to room temperature, and protected by high-purity N2 gas throughout the process, a black carbon airgel was obtained, which was nitrogen-doped graphene/carbon nanofibers loaded with monatomic iron. composite nanomaterials.
  8. 根据权利要求1至5任一项所述的一种生物质基氮掺杂石墨烯/纳米碳纤 维轴向复合材料负载单原子铁的制备方法，其特征在于，按以下步骤制备：According to the preparation method of a kind of biomass-based nitrogen-doped graphene/nano-carbon fiber axial composite material loading monoatomic iron according to any one of claims 1 to 5, it is characterized in that, prepared according to the following steps:
    a、铁盐-细菌纤维素的制备：用去离子水反复冲洗0.5g的细菌纤维素薄膜，之后将清洗干净的细菌纤维素薄膜完全浸入300ml浓度为0.1mol/L的硝酸铁溶液中，同时向该溶液中投入4.0g尿素并充分搅拌，使尿素完全溶解且溶液完全浸没细菌纤维素，待浸入完全后取出细菌纤维素薄膜，即为铁盐-细菌纤维素链状高分子化合物；a, the preparation of iron salt-bacterial cellulose: rinse the bacterial cellulose film of 0.5g repeatedly with deionized water, then completely immerse the cleaned bacterial cellulose film in 300ml concentration of 0.1mol/L ferric nitrate solution, at the same time Put 4.0g of urea into the solution and stir fully to make the urea dissolve completely and the solution is completely submerged in the bacterial cellulose. After the immersion is complete, take out the bacterial cellulose film, which is the iron salt-bacterial cellulose chain polymer compound;
    b、负载单原子铁的氮掺杂石墨烯/纳米碳纤维轴向纳米复合材料的制备：将步骤a中得到的铁盐-细菌纤维素链状高分子化合物置于冰箱中完全冷冻成固体，接着对冻结后的样品置于冷冻干燥机中进行冷冻干燥，得到细菌纤维素与白色絮状尿素的气凝胶；最后，将所得白色气凝胶置于管式炉中，以5℃/min的速率缓慢加热至1000℃并保温1小时，自然冷却至室温，全程通高纯N 2气保护，得到黑色的碳气凝胶，即为负载单原子铁的氮掺杂石墨烯/纳米碳纤维轴向复合纳米材料。。 b. Preparation of nitrogen-doped graphene/carbon nanofiber axial nanocomposites loaded with monoatomic iron: the iron salt-bacterial cellulose chain polymer compound obtained in step a is completely frozen into a solid in a refrigerator, and then The frozen sample was placed in a freeze dryer for freeze-drying to obtain an aerogel of bacterial cellulose and white flocculent urea; finally, the resulting white aerogel was placed in a tube furnace and heated at a temperature of 5°C/min. Slowly heated to 1000°C and held for 1 hour, cooled naturally to room temperature, and protected by high-purity N2 gas throughout the process, a black carbon airgel was obtained, which was nitrogen-doped graphene/carbon nanofibers loaded with monatomic iron. composite nanomaterials. .
  9. 一种生物质基氮掺杂石墨烯/纳米碳纤维轴向复合材料负载单原子铁，其特征在于根据权利要求1-8任一所述方法制备得到的，所述的轴向复合材料中石墨烯沿碳纤维两侧生长，形成同轴复合结构。A biomass-based nitrogen-doped graphene/nano-carbon fiber axial composite material loaded monoatomic iron, characterized in that it is prepared according to the method described in any one of claims 1-8, and the graphene in the axial composite material It grows along both sides of the carbon fiber to form a coaxial composite structure.
  10. 一种根据权利要求7所述生物质基氮掺杂石墨烯/纳米碳纤维轴向复合材料负载单原子铁作为电催化水解制氢的催化剂材料的应用。An application of the biomass-based nitrogen-doped graphene/nano-carbon fiber axial composite material supporting monoatomic iron as a catalyst material for electrocatalytic hydrolysis hydrogen production according to claim 7.
PCT/CN2021/143577 2021-12-23 2021-12-31 Preparation, product and use of biomass-based nitrogen-doped graphene/nano carbon fiber axial composite material loaded with monatomic iron WO2023115637A1 (en)

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